Myrcene-methacrylonitrile adducts

ABSTRACT

There is provided a novel adduct of myrcene and methacrylonitrile which is useful as an odorant in the perfume industry. The adduct possesses a sweet floral odor suggestive of nasturtium, and moreover, possesses a remarkable stability to oxidation.

United States Patent 191 Dahill, Jr.

m1 '3,714;220 [451 Ja n.30, 1973 [54] MYRCENE-METHACRYLONITRILE ADDUCTS[75] Inventor: Robert T. Dahill, Jr., Perth Amboy,

[73] Assignee: Givaudan Corpoartion, Clifton, NJ.

[22] Filed: Dec. 29, 1969 [21] Appl. No.: 888,956

[52] US. Cl "260/464, 252/522 [51] Int. Cl ..C07c 121/48 [58] Field ofSearch ..260/464; 252/522 [5 6} References Cited UNITED STATES PATENTS2,375,937 5/1945 Miller et al. ..260/464 3,030,384 4/1962 Sommerville..252/522 X 3,168,550 2/l965 Blumenthal ..260/464 8/1966 Blumenthal..252/522 X Primary Examiner.loseph P. Brust Alt0rneyCifelli and Behr[571 7 ABSTRACT 1 Claim, No Drawings MYRCENE-METHACRYLONITRILE ADDUCTSDESCRIPTION OF THE PRIOR ART SUMMARY OF THE INVENTION There is provideda novel adduct of myrcene and methacrylonitrile which possesses a soft,floral odor which has not been observed in any nitrile heretofore.

proportion of reagents charged. The progress of the The adduct is amixture of isomers of the following structural formulas The novel adductpossesses remarkable stability to light and air, and this stabilitycombined with its lack of color makes it useful as a base for perfumes.The novel adduct of the present invention is produced by reacting thecomponents at elevated temperatures in an autoclave.

DESCRIPTION OF THE PREFERRED EMBODIMENTS Myrcene and methacrylonitrileare charged into an autoclave with a trace of a free radical suppressantsuch as hydroquinone and the like. There may be utilized eitherequimolar proportions, an excess of myrcene or an excess ofmethacrylonitrile. For purposes of large-scale production it ispreferred to utilize an ex-.

cess of methacrylonitrile since this reagent is cheaper. However, theprogress of the reaction is not affected substantially thereby and theuse of excess methacrylonitrile is by no means critical. While thereaction may be carried out in any reaction-inert solvent, for example,hydrocarbon solvents such as hexane, benzene, toluene, xylene, and thelike, it is preferred to carry out the reaction in the absence ofsolvent.

The reaction vessel is purged of oxygen, suitably by charging thesupernatant cavity witha reaction-inert gas, such as nitrogen, to apressure of, say, p.s.i., and releasing the pressure from about 2 toabout 4 times. In view of the volatility of the reagents, vacuum shouldnot be used to remove the air.

The reaction mixture is then heated to a temperature of from about 50 toabout 300 C. during which heating there is generated an initialpressureof between and 50 p.s.i. It is preferred, however, to operate at atemperature of between 125 and 165 C. at a pressure of from about 30 toabout40 p.s.i. The actual pressure generated will depend upon the amountof reagents charged. The reaction is continued until completion whichwill involve a time period of from about 1 to about 30 hours, dependingupon the temperature and reaction is followed .by gas liquidchromatography, suitably using an SE 30 column at'225 C.

Upon completion of the reaction, the autoclaveis cooled, and thereactionproduct'separated'from the unrcacted starting materials bydistillation under low vacuum. It is preferred to utilize-a water pumpvacuum; that is to say, a vacuum of between 10 and 20 mm of Hg. Afterremoval of the unreacted starting materials, the residue is furtherpurified by distillation. It is preferred to distill using afractionating column,

suitably .a column packed with glass helices at a moderate vacuum; thatis to say, a vacuum of between about 1 and 0.1 mm. ofHg.

The product of the present invention has an unex- .pected and unusualnasturtium-like floral odor of great interest to perfumery compounders.The product is of utility as a perfume base. Various compositionsutilizing the product would be available to one skilled in the perfumecompounders art. However, for purposes of exemplification and not forpurposes of limitation there is shown in Table I below a typicalcomposition utilizing the productsof' the present invention.

TABLE I Bergamot oil I 125 Coumarin 10% in DEF l3 Geraniol 50 Gum BalsamPeru 25 Ionone Beta I3 Lime oil 62 Linalool Linalyl acetate Orange oil.sweet 75 Sandela' I25 Versalide 37 Ylang Bourbon I 253-Cyano-3-methyland 4-Cyano-4-methyl-l-(4- v methyl-3- 1pentenyhcycloheiene 250 Diethylphthalate Registered trademark ofGivaudan Corp. for isocamphylcyclohexanol Registered trademark ofGivaudan Corp. for l, 1,4,4-tetramethyl-6- ethyl-7 -acetyl-l ,2,3 ,4,-tetrahydronaphthalene TABLE II Odor 1 Smooth floral odor.

EXAMPLE 1 A mixture of 426 g. of myrcene, 178 g. of methacrylonitrileand a trace of hydroquinone is charged into a one-liter stainless steelautoclave equipped with an agitator and a gague reading to 300 pounds.Nitrogen pressure is applied and released 3 times. The mixture is heatedwith good-agitation to a temperature of 150 C. for 8 hours. The progressof the reaction is monitored by gas liquid chromatography'on an SE 30column at 225 C. The autoclave is cooled and the reaction mixtureremoved. This'mixture is distilled under water-pump vacuum to remove theunreacted starting materials. The residue is then distilled under a6-inch fractionating column packed with glass helices to yield thedesired adduct consisting of 3- cyano-3-methyl-and4-cyano-4-methyl-1-(4-methyl-3- penthyl) cyclohexene. B.p. 103 (0.5 mmof Hg.) yield,249g, (64 percent based on unrecovered myrcene). n 1.4826,VPC homogeneous on SE 30 at 225 C. (Purity 97 percent) LR. 3.50, 4.50,6.02, 6.97, 7.31, 7.33 microns NMR 4. 601- (1 olefinic proton) (1olefinic proton) ll acrylonitrile Ill crotononitrile lV acrylonitrile Vmethacrylonitrile VI crotononitrile.

It was the surprising result of this comparison that while all of theproducts possessed odor, only one, that of the present invention,possessed an, odor of the nature and strength to be useful to theperfume compounders. There results are summarized in Table lll below.

TABLE III lnrlumors evaluation Unusual nnstnrtlumilornl o lor of much Ninterest in pcrlunwry.

Gemini) oily floral odor,

CN of no value in I and peri'umery.

Spicy-phenolic odor, W o CN no vlaue in perfumery.

and

l weak, spicy odor, of no value in pertumery. and i 1 I Weak, licoriceodor of A A no value in perlumery, and

l r I I C N I I Weak, burnt odor, of no A A value in porlumery.

and

WW 7 I v nml

